Curing systems for vinylidine fluoride elastomers

ABSTRACT

A CURABLE AROMATIC COPOLYMER COMPOSITION COMPRISING VINYLIDENE FLUORIDE COPOLYMER, AT LEAST ONE QUATERNARY PHOSPHONIUM OR AMMONIUM COMPOUND, AND AT LEAST ONE ELASTOMERIC HYDROXY OR AMINO COMPOUND HAVING AN OXIDATION POTENTIAL NOT MORE THAN 1.5 VOLTS WITH RESPECT TO A STANDARD CALOMEL ELECTRODE AND PROCESS FOR THE CURING THEREOF IN THE PRESENCE OF AN INORGANIC ACID ACCEPTOR CAPABLE OF GENERATING WATER UPON REACTING WITH HYDROGEN FLUORIDE.

A il 11, 1972 u. PATEL ETAL 3,655,727

CURING SYSTEMS FOR VINYLIDINE FLUORIDE ELASTOMERS Filed Jan. 16, 1970 40/4 757/844? Y HYDROX/ZZE A644 m/vJ/ (1847a JOHN E Ala/5e 477 fWEYS United States Patent M 3,655,727 CURING SYSTEMS FOR VINYLIDINE FLUORIDE ELASTOMERS Kalyanji U. Patel, St. Paul, and John E. Maier, Woodbury, Minn., assignors to Minnesota Mining and Manufacturing Company, St. Paul, Minn. Continuation-impart of application Ser. No. 831,295, June 9, 1969, which is a continuation-in-part of application Ser. No. 802,917, Feb. 27, 1969, which in turn is a continuation-impart of application Ser. No. 753,618, Aug. 19, 1968. This application Jan. 16, 1970, Ser.

Int. Cl. C0815 27/08 US. Cl. 260-470 P 19 Claims ABSTRACT OF THE DISCLOSURE A curable aromatic copolymer composition comprising vinylidene fluoride copolymer, at least one quaternary phosphonium or ammonium compound, and at least one elastomeric hydroxy or amino compound having an oxidation potential not more than 1.5 volts with respect to a standard calomel electrode and process for the curing thereof in the presence of an inorganic acid acceptor capable of generating water upon reacting with hydrogen fluoride.

This application is a continuation-in-part application of U.S. application Ser. No. 831,295, filed June 9, 1969, which is a continuation-in-part of US. application Ser. No. 802,917, filed Feb. 27, 1969, which is a continuation-inpart application of U8. application Ser. No. 753,618, filed Aug. 19, 1968, all now abandoned.

This invention relates to a method for crosslinking fluorinated polymers and crosslinking compositions for use therein. In one aspect this invention relates to a new vulcanization admixture for producing a crosslinked product of improved compression set. In another aspect this invention relates to the modification of the characteristics of linear saturated polymers containing halo-gen substituents on the carbon atoms, particularly those polymers having elastomeric properties.

In general, linear polymers are thermoplastic in nature and exhibit continuous flow under the influence of heat and pressure. Such polymers can be resoftened as often as desired and are usually soluble in selected solvents. However, crosslinked or vulcanized polymers are generally thermoset, i.e. insoluble in most solvents and incapable of being resoftened without decomposition, since they are permanently hardened. A linear polymer may nevertheless contain a small number of crosslinkages without losing its thermoplastic properties. It is often desirable to convert thermoplastic polymers into crosslinked polymers or into partially crosslinked polymers in order to decrease their solubility and thermoplastic flow properties and to obtain a harder and tougher product. The crosslinking of elastomers is commonly referred to as vulcanization.

Among the most difficultly vulcanizable thermoplastic polymers are those prepared by the polymerization of halogenated monoolefins, such as, for example, the copolymers of chlorotrifluoroethylene and vinylidene fluoride, the copolymers of perfluoropropene and vinylidene fluoride and the terpolymers of perfluoropropene, vinylidene fluoride and tetrafluoroethylene. Many of these fluorinated thermoplastic polymers have unique and valuable properties. In some case, when it is desired to retain these properties and at the same time decrease the thermoplastic flow and solubility, and the polymers are crosslinked. Such crosslinking has heretofore resulted in a relatively high compression set of the final product,

e.g. a compression set of more than 30% after 24 hours at 400 F. (205 C.).

One major utility of vulcanized, highly fluorinated elastomers lies in their use as gaskets, O-rings and the like, for containing fluids under pressure at elevated temperatures, as, for example, in hydraulic systems in aircraft, or as components of reactors in the processing of chemicals. In use, the elastomer is continually compressed for extended period of time. If during use the elastomeric part becomes permanently deformed, i.e., undergoes compression set, the seal fails causing leakage. In general, the higher the temperature and the longer the elastomer is under compression, the greater the degree of compression set and accordingly the greater the danger of equipment failure.

It is therefore an object of this invention to provide a new and improved crosslinking system.

Another object of this invention is to provide a new curable, fluorinated polymer admixture.

Still another object of this invention is to provide a method for crosslinking vulcanizable fluorinated elastomers.

A further object of this invention is to provide a cured fluorinated elastomer with improved physical properties, including low compression set.

An important object of this invention is to provide a crosslinking or curing system for fluorinated elastomers which utilizes relatively low concentrations of curing agent but which still is capable of conveniently producing a cured elastomer having low compression set and having a minimal amount of residual, unreacted curing agent, thereby reducing the undesirable tendency of the cured elastomer to further cure during actual use, aging or testing.

Other objects and advantages of the present invention will become apparent to those skilled in the art from the accompanying description and disclosure.

Accordingly the invention provides an elastomeric composition curable in reactive association with an inorganic acid acceptor capable of generating water upon reacting with hydrogen fluoride to produce a cured elastomer having low compression set. The curable elastomeric composition or admixture comprises the following components:

(a) A fluorinated elastomeric copolymer of vinylidene fluoride and at least one terminally unsaturated fluoromonoolefin containing at least one fluorine atom substituent on each double bonded carbon atom, each carbon atom of said fluoromonolefin being substituted only with fluorine, chlorine, hydrogen or a lower fluoroalkyl or fluoroalkoxy radical, at least 10 percent of the chain carbon atoms of said copolymer being CH units;

(b) At least one quarternary ammonium or quarternary phosphonium compound of the formula wherein Q is a phosphorus or nitrogen atom, X is an anion (e.g. sulfate, acetate, phosphate, halide, hydroxide, alkoxide, phenoxide, etc.), in is the valence of anion X (e.g. l-3), R is an alkylene radical having from 2 to 12 (preferably 2 to 6) carbon atoms or a phenylene dialkylene radical having from 8 to 12 carbon atoms (e.g. -CH C H CH R is an alkyl radical having from 1 to 12 (preferably 1 to 6) carbon atoms or an aralkyl radical having from 7 to 12 carbon atoms, and wherein R, R and R represent alkyl radicals having from 1 to 18 (preferably 1 to 12, most preferably 1 to 6) carbon atoms;

(0) At least one aromatic hydroxy or amino compound which has an oxidation potential no more than 1.5 volts with respect to a standard calomel electrode; and

(d) In a preferred embodiment the curable composition also includes at least one compound which is stable in the absence of water at temperatures below about 75 C. and which at a temperature above 125 C. and in the presence of water releases a basic nitrogen-atom containing compound having at least one hydrogen atom bonded to said basic nitrogen atom. Preferably the compound is one which releases a primary or secondary amine, a hydrazine or ammonia.

Although the mechanism is not fully understood, the combination of of each of the above components in vulcanization system displays an effect not attributable to any one specific component or any combination less than the required components of the above curing system, resulting in a drastic reduction in the compression set of the cured product, i.e. less than 20 percent compression set and generally less than about percent compression set after exposure to 400 F. (205 C.) for 24 hours, and also resulting in a complete cure with essentially no residual effective curing agent, all of which is accomplished with a low concentration of curing ingredients, as will be hereinafter discussed. Another valuable attribute of the above curing system is the greater latitude permissible in the formulation, and minor changes in the proportions of the components within the specified limits do not drastically effect the processability, particularly its ability to be milled without scorching and yet to cure rapidly.

The vulcanizable polymers which are cured according to this invention are linear, saturated, fiuorinated polymers which contain reactive substituents selected from the group consisting of hydrogen, fluorine and chlorine and which are at least half halogenated. By half halogenated is meant that at least one half of the carbon bonded hydrogen atoms of the analogous nonhalogenated polymer are replaced by halogen. The preferred vulcanizable polymers are at least half fiuorinated; however, it is critical that the polymer chain include CH units. Homopolymers of tetrafluoroethylene and other perfluorinated olefins, and copolymers thereof with other perfluorinated comonomers require very high temperature to effect crosslinking and are not within the scope of this invention.

Linear fiuorinated elastomers generally contain disordered, saturated, fluorinated carbon chains which include a substantial number of -CH units, usually at least 10 percent of the chain carbon atoms. Disorders in the carbon chains is ordinarily achieved by the copolymerization of at least two monoolefinic compounds of the type hereinafter described. When one of the monoolefinic compounds contains an unsaturated chain of three or more carbon atoms, alkyl side groups, e.g. methyl, ethyl, etc., are present in the final polymer, and these alkyl groups are preferably perhalogenated, most preferably perfluorinated. Points of unbalance in the carbon chain, which are necessary for elastomeric properties, are provided by these side groups. Such side groups cause a bending of the linear carbon chain and thus provide additional degrees of freedom in space, producing an unsymmetrical chain carbon atom to which they are attached. However, unbalance is also provided by the presence of other unsymmetrical units in the linear carbon chain, such as CFC1. Irrespective of the units providing such points of unbalance, whether by two physically different substituent atoms or by a side group on a chain carbon atom, at least 10 percent of the chain carbon atoms should be unbalanced.

The linear, saturated, fiuorinated carbon chain in the elastomers may also contain chlorine substituents, provided a single chain carbon atom has no more than one chlorine attached thereto to produce instability or to influence the chemical nature of the elastomer. The presence of more than one chlorine substituent on a single chain carbon atom produces a point of rigidity in the chain, decreasing the flexibility of the chain and the elastomeric properties accordingly.

Among the saturated polymers which may be crosslinked in accordance with this invention are the fiuorinated elastomeric copolymers of chlorotrifluoroethylene, vinylidene fluoride, 2-chloroperfiuoropropene, a fiuorinated methyl vinyl ether, perfiuoropropene, tetrafluoroethylene, l-hydroperfluoropropene (i.e. CFH=CFCF dichlorodifluoroethylene, trifluoroethylene, 1, l-chlorofluoroethylene and vinylidene chloride. These monoolefins may be copolymerized with each other in groups of two or more. They may also be copolymerized with other olefinic compounds such as ethylene. The preferred elastomers are copolymers of vinylidene fluoride with at least one terminally unsaturated fluoromonoolefin containing at least one fluorine atom substituent on each double bonded carbon atom, each carbon of said fluoromonoolefin being substituted only with fluorine, chlorine, hydrogen or a lower fluoroalkyl (e.g. perfluoroalkyl) or fiuoro'alkoxy r-adical, particularly perfluoropropene, tetrafluoroethylene, chlorotrifiuoroethylene and l-hydroperfluoropropene. Particularly preferred are the fiuorinated elastomers produced by copolymerizing perfluoropropene and vinylidene fluoride, as described in US. Pat. Nos. 3,051,677, issued Aug. 28, 1962 and 3,318,854, issued May 9, 1967, and those terpolymers produced by copolymerizing perfluoropropene, vinylidene fluoride and tetrafluoroethylene as described in US. Pat. No. 2,968,649, issued Jan. 17, 1961. The elastomeric copolymers of perfluoropropene and vinylidene fluoride having between about 15 and about 50 mole percent perfluoropropene are outstanding in this respect.

A critical ingredient in the final curable composition is at least one oxidizable aromatic hydroxy or amino compound which has an oxidation potential no greater than 1.5 volts preferably no greater than 1 volt, with respect to a standard saturated calomel electrode and which is free of electron attracting groups as substituents on the aromatic nucleus. Oxidation potentials are conveniently measured by conventional cyclic voltammetry, using a platinum electrode and the compounds at concentrations of about 10* mol per liter in substantially anhydrous dimethylformamide, including 0.2 mole/liter of a soluble conductivity aid, such as sodium perchlorate. Among those compounds oxidizing between about 1 and 1.5 volts in this test are phenol, meta-cresol, resorcinol, catechol, bis-phenol A [i.e. 2,2-bis (p-hydroxyphenyl) propane] and p-bromophenol. Among those compounds oxidizing at no more than about 1 volt are p-dihydroxybenzene, odihydroxybenzene and pyrogallol. The preferred aromatic hydroxy or amino compounds are represented by the general formula:

ArZ

wherein Z represents an OH or NH aromatic ring substituent, n represents an integer from 1 to 2, and Ar represents an n-valent aromatic nucleus (e.g. phenyl, naphthyl). Preferably the aromatic nucleus is unsubstituted but it may also be substituted. If substituted, electron-donor groups such as alkyl, alkoxy, aryl, aryloxy, and aralkyl are preferred, since electron attracting substituent groups such as halogen, nitro, carboxyl, and the like result in an aromatic compound which, unless used with a more severe curing cycle, tends to produce a cured elastomer with higher compression set. Hydroquinone, i.e. p-dihydroxybenzene, is a particularly preferred compound.

The composition also includes at least one quaternary ammonium or quaternary phosphonium compound of the formula recited earlier. Typical quaternary ammonium compounds include:

6 and the corresponding salts thereof, such as tetrabutylamis not fully understood. Existing evidence suggests that the monium bromide. Quaternary phosphonium compounds initial press cure involves a base-catalyzed release of hyinclude, for example, drogen fluoride to generate double bonds in the polymer, 7 these double bonds then providing a limited number of [(C4 o)4 ]BR-, and crosslinks between the polymer chains which serve to sta- CH bilize the shape and form of the polymer, while the subsequent post cure step results in the formation of further ethylenically unsaturated structures which combine to hctfilhljh I form benzenoid crosslinks of high thermostability. This is s-o OH 10 consistent with our findings that a variety of compositions function as curing or crosslinking agents, acting to aid in (cfishpnacetfltefl the release of hydrogen fluoride. Most free primary or sec- [(C4H9)4P+][OH-] ondary aliphatic amines (insofar as they are not In themselves amine generators), free hydrazine or free ammonia The quaternary compounds are conveniently admixed are not Slut-able as curlng agents, and n use s Such with the fiuoroelastomer as a solution in an inert, volatile reshh eithel: too rapid afmre fate 0r o cure at a l such as methanol, although many of h It is convenient to conslder the preferred carbonyl pounds can also be introduced to the curable elastomer addhct as dew/eh from h reaction of a Carbonyl in the form of finely divided solids. The salts of these P an P1111116, and In In cases the adduct may be quaternary compounds are generally preferred over the prepared 1nth1s manner. However, carbonyl adducts withcorresponding hydroxides because of their better stability. 1n the FP of thls lnvefl'tlon y 2115? be P pa y A f th r component i the fi l curing recipe is an alternative syntheses wh1ch are chemically equivalent. inorganic acid acceptor capable of generating water upon Carbonyl adducts which thermally p eactlofl With reacting with hydrogen fluoride. Suitable acid acceptors P more molechles 0f j generate the a ine are bases and include magnesium oxide, lead oxide (lithh In the fhrmhlatloh as q Y f r xample hexylarge, P1 0), dib i lead phosphite and Zinc oxide, with rsocyanate and hexane carbodnmlde as well as hexylcarmagnesium oxide being preferred. The acid acceptors are hamate, N'hexylacetamlde are consldered herein as q d i amounts ranging from 2 to 25 parts per 100 parts alent carbonyladducts of hexylamine and either carbon of polymer, In ddi i an optional base is generally dioxide or acetic acid, smce they liberate the same amine,

desired as a cure accelerator. These optional bases are asis Showh hythe following reaction:

basic compounds and include inorganic oxides and hydroxides such as calcium hydroxide, barium carbonate, strontiurn hydroxide, and the like. The optional bases are preferably used in amounts ranging from 0.5 to 10 parts per 100 parts of polymer.

Although not necessary, the composition preferably CH3cONHc6H13+H2O C6H13NH2+CH3CO2H contains at least one aromatic amine (primary, secondary (CSHBNHhPzOiS not an equivalent carbonyl adduct tert 1ary), ahphahc ternary amlhe, or a compound of hexylamine, since it does not liberate a carbonyl deriva whlch 13 Stable m the absehc? of Water at temperatures 40 tive, but is regarded as a useful amine generator because below about 75 C. and which at temperatures above it generates a Suitable amine about 125 C. 1n the presence of Water generates a basic The carbonyl moiety of the carbonyl adduct is general mtrhgeh atorh'cohtalhlhg compound a compouhd ly derivable from carbon dioxide, carboxylic (including havlng a P b In Water of no more than ahout havlhg polycarboxylic) acids, aldehydes or ketones. The preat least one hydrogen atom bohded to 531d haslc mtrqgen ferred aldehydes and ketones and carboxylic acids are atom (pheferably gehehates a prlmary or secondary amlhe, represented by the general structural formulae: R @O; a hydrazlne or ammonla), all of WhlCh will be referred to s wherein 6 represents hydrogen, an alkyl herem asfamlnesfi Amlfles g too hlgh a molecular (including cycloalkyl) radical of 1 to 25 (preferably 1 to Welght dlfhle less effihlehfly through the hhorocarboh 12) carbon atoms, an aralkyl radical of 7 to 25 carbon polymer during the curlng process, thus tendlng t result atoms, or an aryl (including alkaryl) radical of 6 to 25 in uneven cure and inferior physicalproperties of the recarbon atoms TWO alkyl radicals may be combined to sultmg vulcanizate. Generally, a satlsfactory cure can be f an ahcyclic divalent radical, cyclohexanone,

obtained most effectively with an amine having a molecular weight of not more than about 1000, and in most cases an amine having a molecular weight of not more than about 500 is preferred. In order to obtain optimum physical properties, particularly resistance to changes dur- Exemplary adducts include:

ing aging and resistance to solvents, it is desirable that the A1dehydeammhia adducts, amine equivalent weight (i.e. total molecular weight N divided by the number of basic nitrogen atoms in the molecule) in the free amine should be no greater than about 500, and preferably no greater than about 300.

Hz (EH2 C Hg For purposes of this discussion, compounds which gen- GCHEO crate a baslc nitrogen atom-contaming compound, while considered amines as mentioned above, will also be 6 20 more particularly referred as amine generators, the preferred amine generators being further characteized as (hexamethylene tetramine) amine adducts or carbonyl adducts. It 1s to be understood that while the amine generators of this invention y pr1m ry amine adduCtS, -g-, must be capable of generating an amine in the presence R6 :0 H NR7 R6CH:N 7 of water, certain of the useful amine generators are also CH 2 R +H20 capable of generating an amine in the presence or (3) Aldehydksecohdary ahhhe adducts, absence of water, eg carbamates, urethanes, carbodi- R26CHCH=O+HNR7R8 R26C=CHNR7R8+H2O rmrdes, thiourethanes, etc.

The mechanism of curing saturated copolymers of '(4) Ketone pnmary amme In the above formula R is as defined earlier; R and R may be selected independently from the group consisting of aromatic radicals of 6 to 25 (preferably 6 to 12) carbon atoms, unsubstituted, saturated aliphatic radicals of 1 to 25 (preferably 1 to 18, most preferably 1 to 6) carbon atoms (e.g., alkyl and cycloalkyl) and araliphatic radicals of 7 to 25 (preferably 7 to 12) carbon atoms.

While the above illustrations exemplify monoamino compounds, polyamino (including diamino) compounds are equally useful and in some cases preferred. For example, in place of ammonia, hydrazine (H NNH can be used; in place of hexylamine, H N(CH CH hexamethylenediamine, H N(CH CH NH can be used; in place Of C H5NHC gH 7, C6H5NHC36H72NHC6H5 can bfi used, and so on. At least one of the amino groups is combined in the form of a carbonyl adduct, but alternatively more than one, or all, may be so combined. For simplicity and convenience, a symmetrical compound is preferred, but an unsymmetrical compound, such as 6-methylaminohexylamine, is equally suitable.

It should be noted that aldehyde and ketone compounds, to react with a secondary amine in the preparation of a carbonyl adduct, must have at least one hydrogen substituent on at least one carbon atom adjacent to the carbonyl carbon. Carbon-bonded substituents such as hywherein R is as defined above, In is 0 or 1 and n is 2 to 36, preferably 2 to 6; or a carbamate of the general forwherein Y is a hydrogen atom, an alkyl radical of l to 6 carbon atoms or an aryl radical of 6 to 12 carbon atoms (preferably Y is a hydrogen atom), X is a carbamic radical, and n is 2 to 36, preferably 2 to 6.

The amine generator may be incorporated directly into the elastomeric material to be cured or, in the case of carbonyl adducts, the respective components or precursors thereof may be introduced into the curable elastomeric material when their reaction in situ occurs to form the desired amine adduct, for example, during the milling or mixing of the rubber formulation prior to cure.

A particularly useful amine generator of the present invention is cinnamylidenetrimethylenediamine. The most preferred amine generators are produced in known manner by reaction of an aliphatic or cycloaliphatic diamine with an aldehyde or with carbon dioxide. Illustrative adducts of the diamine with carbon dioxide (i.e. carbamates) are shown in US. 3,096,314 and described in conjunction with the curing of highly fluorinated elastomers.

The following are examples of aldehyde-diamine adducts useful in the practice of the invention as well as the aldehydes and amines from which they are produced.

droxyl or halogen (e.g., chlorine or fluorine), generally in- Other useful amine generators include complexes of terfere neither with the formation of carbonyl adducts nor amines with transition elements, such as nickel, iron and with the ability of such adducts to function as curing agents.

The most preferred amine generators of this invention are either dialdehyde aliphatic diamine adducts (i.e. dialdimine) of the general formula:

triphenylbismuthine, triphenylarsine, dibutyl tin sulfide and tributylphosphine, may also be employed in similar fashion as the amine.

The quaternary compound, alone or premixed with a suitable amine, may be conveniently milled into the elastomer gum stock. Thus mixed, the stock can be stored at room temperature (i.e. about 80 F. or 27 C.) for extended periods, e.g. at least six months. Prior to curing, the oxidizable aromatic hydroxy or amino compound and the acid acceptors are milled into the stock, after which the storage life at ambient temperatures is more limited and molding or extruding the product within about two to three weeks is recommended. Of course, all of the components of the curing system may be admixed prior to their incorporation into the 'elastomer without departing from the scope of this invention. It may also be desirable in some instances to employ retarding agents, plasticizers, fillers, and other conventional additives.

The proportions of components of the curing system are set forth below in parts by weight. (All amounts referred to herein are in parts per 100 parts of polymer abbreviated pphr., unless otherwise indicated.) These proportions are general ranges and the particular amount for each particular cure, time and temperature will become apparent to those skilled in the art.

TABLE L-FORMULATION LIMITS Component: Parts phr. (range) Amine 1 -2.5

Quaternary compound 0.05-0.5

Acid acceptor 2-25 Optional base 0-10 Oxidizable hydroxy or amino compound 0.1-2

1 Preferably 0.1-2.5.

Although low compression set elastomers are obtained within the aforementioned formulation limits, elastomeric products having compression set values of or less may be obtained by varying the relative amounts of the components listed in Table I within the specified ranges. Preferably the quaternary ammonium or phosphonium wherein x is the amount of hydroxide in pphr., y is the amount of amine in pphr., x being greater than or equal to 0.05 and y being greater than or equal to 0.25.

Of the acid acceptors, magnesium oxide is preferred. At least about 2 pphr. is required to provide a reasonable level of cure and rate of cure. The maximum amount for the acid acceptor as listed in Table I is not critical, as much as 50 to 60 pphr. producing a usable but hard stock. Generally, however, no more than about 25 parts is necessary for adequate curing. Alternatively, zinc oxide, litharge or dibasic 'lead phosphite may be used in approximately the same proportions, and calcium oxide may sometimes be used.

In addition to the above acid acceptor, when an optional base is desired as an accelerator, it is usually present in amounts of from about 0.5 to 10.0 pphr. Calcium hydroxide is preferred, barium carbonate being milder and generally being used in somewhat larger amounts.

Fillers are often added to the polymers discussed above to improve the molding characteristics and other properties, When a filler is employed it is added to the vulcanization recipe in amounts of up to about 100 parts pphr., preferably between about 15 and about 50 parts. Examples of fillers which may be used are reinforcing thermal grade carbon blacks or non-black pigments of relatively low reinforcement characteristics such as clays, barytes, etc. Plasticizers, softeners and processing aids, preferably esters or ketones, may also be added if desired.

In accordance with this invention, the desired amount of the components of the crosslinking system is added to the unvulcanized fluorocarbon polymer (i.e. gum stock) and is intimately admixed therewith or compounded by employing any the usual rubber mixing devices, such as Banbury mixers, roll mills, or any other convenient mixing device. It has been found that a tworoll rubber mill equipped with heat exchange means, e.g. cored chambers for cooling, is particularly suitable since the heat generated by the high shearing forces in mixing can be dissipated and the temperature more accompounds are added in solution in a solvent such as methanol.

Use of larger amounts of amine tends to increase the cure rates and provide a tighter cure. However, excessive amounts may promote excessive curing or aging and to effect, for example, higher compression set values and lower elongation values. Generally, when an amine is used, the lowest amount of amine which will provide the desired rate of cure and level of compression set at practical curing temperatures is preferred and, in fact, amounts much in excess of about 2.5 pphr. are undesirable because of the adverse effect on heat aging properties.

Quaternary ammonium and phosphonium compounds, when used in amounts as small as 0.05 pphr., produce a measurable acceleratory effect on cure rate at a given amine concentration. An excess of the quaternary compound, over 0.4 pphr., particularly when more than about 0.5 pphr., tends to elfect an overcured vulcanizate, although in general the higher molecular weight quaternary compound can be used in greater amounts than those of lower molecular weights. Generally, the lower the amount of amine employed, the greater the optimum amount of the quaternary compound. The preferred proportions in an exemplary system using tetrabutylammonuim hydroxide and cinnamylidene trimethylenediamine are illustrated in the drawings, and are represented by the shaded area of the graph. The following equation describes these preferred proportions:

curately regulated with this device or with devices providing other means for temperature control.

For best results the temperature of the mixture on the mill is not allowed to rise above about 250 F. C.) and is not allowed to fall below 30 F. (0 0.). During miling it is necessary to distribute the crosslinking agent uniformly throughout the curable polymer. However, it is also desirable to prevent extensive crosslinking in the compounding step since most of these fluorinated polymers cannot be molded or extruded after a substantial amount of crosslinking has taken place.

The curing process typically comprises pressing the compounded mixture in a mold and then baking the pressing in an oven. Pressing of the compounded mixture (press cure) is conducted at a temperature between about 200 F. (95 C.) and about 450 F. (230 C.), preferably between about 300 F. C.) and about 400 F. (205 C.) for a period of from 1 minute to about 15 hours, usually from 5 minutes to 30 minutes. A pressure of between about 7 and about 210, preferably between about 35 and about 70, lag/cm. is imposed on the compounded mixture in the mold. The molds may be first coated with release agents, such as a silicone oil, and prebaked. The molded vulcanizate is then usually post cured (oven cured) at a temperature between about 300 F. (150 C.) and about 600 F. (315 C.), usually at about 400 F. (205 C.) for a period of from 2 hours or less to 50 hours depending on the cross-sectional thickness of the sample. The temperature during the post cure is usually raised gradually from the lower limit of the range to the desired maximum temperature selected. The maximum temperature used is preferably about 500 F. (260 C.) and is held at this value for at least 24 hours.

The following examples are offered as a better understanding of the present invention and was not to be unnecessarily construed as limiting the scope thereof. In the tion with a diamine carbamate produces cure fluorinated elastomers which, after 70 hours at only 250 F. (120 C.) have compression set values of 30 to 60%. From the TABLE A Run I IV V Elastomer (CaFs/CFFCHz, 24/76 mole ratio)--- 100 100 100 MgO 10 10 10 Carbon black 20 20 20 Cinnamylidenetrimethylenediamin 2 0. 5 0. 5 Tetrabutyl ammonium hydroxide 0. 2 0. 2 Hydro uinone l 2 1 a( E82- 1 1 1 CaS 0. 0. 5 0. 5 Mooney pt. rise at 250 F. (120 0.) 25 min 25 min 25 min. 330 F. (165 0.) 3. 6 5 6. 0 Compression set:

1 day at 400 F. (205 C.) 10 6 3 7 days at 400 F. (205 C. 32 18 14 7 days at 347 F. (175 C.) 18 7 0 3 days at 77 F. (25 0.) 7 3 6 Tensile at break, p s 1 (kg /c 1 Broke.

*A=data from post-cured sample. **B=data from post-cured sample after accelerated aging (i. e. 10 hours at 316 0.).

examples, indicated results were obtained using the following test methods:

at break, 2 modulus at 100% A-O 125" (3.5 mm elongation. L0.75 (19 mm.

C=2.0 (51 mun). Accelerated aging A5525 (1)) 573-53 exposed for 16 hours at 600 F. Press cure Unless otherwise noted sheets were prepared 3"X 6X0.07 (75X150XL8 mm.) pressed at about 1,000 p.s.i. (70 kg./cm. for 20 minutes at 320 F. (160 C.) for physical property determinations; plugs for compression set were 1" mm.) diameter 0.5" (12.5 mm.) thick, pressed at about pjsji. (140 kg./cm. for minutes at 320 F.

Post cure. Samples were removed from the press and placed in a circulating air oven. The oven was maintained at 300 F. (150 C.) for 2 hours, increased to 350 F. (175 0.) and held for 2 hours, increased to 400 F. (205 C.) and held for 20 hours, then increased to 500 F. (260 0.) and held for 24 hours (unless otherwise noted, see Ex. IX-XII).

EXAMPLE I The interrelated effects on rate of cure, physical properties and stability toward aging due to variations in amounts of amine, quaternary compound, oxidizable aromatic hydroxy or amino compound, and optional base are demonstrated by the results of the tests indicated in Table A.

The data in Table A illustrate the value of using an amine together with a quaternary compound and an oxidizable aromatic hydroxy compound. Run I shows the results obtained with the omission of the quaternary compound, and Runs II-V show results obtained with varying amounts of the quaternary compound in the formulation of this invention. In Run I the compression set is significantly higher than in Runs IIV. In addition, the higher level of amine required in Run I produces much poorer aging, as represented by greatly decreased elongation at break, greatly increased hardness, and an inability to obtain a 100 percent modulus because of the very low elongation due to aging after post cure. This aging is an indication of the manner in which the cured elastorner will function during actual use.

In Example 1 of U.S. Patent No. 2,951,832 a formulation using a diamine adduct both alone and in combinacompression set data in Table A of the present example, a reduction in the temperature from 400 F. (205 C.) to 350 F. (175 C.) results in a decrease of compression set of from 14-24% to 9-12%, and a further decrease of the temperature to 250 F. C.) would clearly still further decrease the compression set values. This illustrates the significant improvement in compression set of the curing formulations of the present invention.

EXAMPLE II The effect on cure results of varying the amount of hydroquinone was observed using a formulation having the following components and the amounts of hydroquinone noted in Table B:

Elastomer (C F /CF =CH 24/76 mole ratio)-l00 parts MgO-IO pphr.

Carbon black-20 pphr.

Ca(OH) --1 pphr.

Cinnamylidenetrimethylenediamine0.5 pphr.

Tetrabutylammonium hydroxide-0.2 pphr.

CaS-0.5 pphr.

TABLE B Hydroquinone Cure (pphr.) Cure conditions results 0 320 F. C.), 20 minutes Blown. 0 395 F. (200 0.), 5 minutes No cure. 0.25 320 F. (160 0.), 20 minutes Good. 0. 5 320 F. (160 0.), 20 minutes Do. 0. 5 395 F. (200 0.), 5 minutes Do. 1.0 395 F. (200 0.), 5 minutes Do. 2.0 395 F. (200 0. 5 minutes Do.

At 0.1 pphr. hydroquinone slightly increased amounts of diamine adduct, tetrabutylammonium hydroxide and/or calcium hydroxide are required to obtain acceptable cure results.

EXAMPLE III Using the following formulation:

Elastomer (C F /OF =CH 24/76 mole ratio)l00 parts.

MgO10 pphr.

Carbon black-20 pphr.

CaS0.5 pphr.

Hydroquinone-Z pphr.

13 several samples were prepared with varying amounts of hexamethylenediaminecarbamate, containing 0.5, 1.0 and 1.5 parts by weight respectively. Each' sample was subjected to a press cure as in Example 1 for 30 minutes at 325 F. (165 C.). In none of the samples was a cure obtained. These samples indicate the need for the quaternary ammonium hydroxide to effect a satisfactory cure in a hydroquinone-containing system for the production of a rubber having good physical properties, including low compression set.

EXAMPLE IV This experiment shows the elfect using various diamine adducts in a standard formulation consisting of:

Elastomer (CgF /CF =CH 24/76 mole ratio)100 parts.

Carbon black pphr.

MgO--10 pphr.

Tetrabutylammonium hydroxide0.2 pphr.

Hydroquinone-l pphr.

The adducts were added in approximately equimolar quantities, the compounded stock milled, molded and post-cured as in Example I, and properties determined as follows:

TABLE CI-Continued Compression set,

Clnnamylldeneethylenedlamlne Clnnamylldenetrlmethylenediamlne 1 0. 5 Cinnamylldenehexamethylenedlamine Trlmethylenediamlneearbamate Hexamethylenedlamlnecarbamate Mooney, 10 point rlse at 167 0., minute Compression set, percent 1 day at 205 C. 6 5 2 6 Tensile strength at break, p.s.l. (kg/cm) A 6 3 322 828 ig Tensile strength at break, p.s.l. (kg/cm?) B 222 figg g8 222 $39 450 510 720 380 420 ulu p- -i. e/ -M {(31) (36) (50) (39) 100% modulus, p.s.l. (kg/cm!) B egg Elongation at break, percent A 240 200 220 260 210 Elongation at break, percent B- 100 90 160 Shore A; hardness, A- 70 70 70 71 70 Shore A: hardness, B 75 71 73 70 74 1 Parts per parts of polymer. A=data from post-cured sample. B=data from post-cured after accelerated aging.

EXAMPLE V To illustrate the equivalence of various aldehyde adducts, mixtures were prepared according to the formulation in Table B except that hydroquinone was maintained at 1 pphr. and various dialdehyde adducts of trimethylenediamine were used each at 0.5 pphr. The materials were molded and post-cured. The compression set data are shown in Table C.

EXAMPLE VI The eflfect of various readily oxidized aromatic amines and phenols is shown in Table D.

A standard formulation was prepared from:

Elastomer (C F /CF =OH 24/76 mole rati0)-100 parts.

Carbon black20 pphr.

MgO-10 pphr.

Tetrabutylammonium hydroxide0.2 pphr.

Cinnamylidenetrimethylenediamine-O.5 pphr.

Aromatic compound-1 pphr.

The materials were milled to a uniform dispersion, then sheets and plugs prepared as described above. Sheets were press cured for 20 minutes at 335 F. (165 C.) and plugs for 30 minutes at 320 F. C.), then post cured and tested. The pertinent results are summarized in Table D.

TABLE D Compres- Tensile 100 Elongasion set percent Modulus, tion, Aromatic compound percent P.s.i. KgJcm. p.s.i. kg./em. percent Phenol 15 1, 880 132 410 29 270 o-Dihydroxybenzene 16 2, 000 140 340 24 270 m-Dihydroxybenzene-. 12 2,050 144 440 31 230 pDihydroxybenzene 6 2,360 165 510 36 200 m-Methyl phenol- 13 2, 560 179 750 52 260 p-Methyl ph IloL- 13 2, 600 182 610 43 230 m-Amiuo phenol. 10 2, 530 177 1, 605 112 140 m-Phenylenedlamine 14 2, 170 152 950 66 190 p-Phenylenediamine. 12 2, 500 175 1, 280 90 180 2,2 b1s(p-hydroxyphe 11 2, 210 157 460 32 250 p-Br phenol*** l9 2, 500 175 370 26 320 "24 hours at 400 F. (205 0.). "Elongation at break. "*Formulatlon includes 3 pphr. Ca(OH) 2.

Aromatic hydroxy and amino compounds containing an EXAMPLE VIII P p when the following elastomeric copolymer is employed:

satisfactory cure under standard curing conditions, or more prolonged or higher temperature press cure.

EXAMPLE VII This example compares the results obtained through use of a variety of amine carbonyl adducts.

A base formulation was prepared consisting of:

This formulation, with the addition of the amount of amine generator indicated in Table B, were milled to a uniform dispersion and samples prepared as indicated in Example I. The pertinent test results are summarized in Table E. The amines liberated by the corresponding amine generators of Table E are set forth in Table F.

an elastomeric copolymer consisting of CFH=CFCF CH CF in a mole ratio of 20/ having a specific gravity of 1.816 at 25 C. and a Mooney Viscosity (ML 1+4, C.) of 90, available under the trade name Tecnoflon-T from Montecatini Edison, S.p.A., Milan, 'Italy.

A formulation is prepared consisting of:

Compression set, [24 hours at 400 F. (205 C.)]-18% Tensile307'0 p.s.i. (215 kg./cm. 100% modulus-1070 p.s.i. (75 kg./cm.

TABLE E Compres- Tensile Elonga- Amount, sion* set, 100% Modulus, tion, Run Amine generator pphr percent p.s.i. Kg./cm.= p.s.1. kgJemJ percent 1 Cyclohexylamine 0. 25 2.-- Z-OH-ethylamine 0.25 3..- Cinnamylidene cyclohexylamine 0. 5 11 2,510 175 440 31 260 4--- Cinnamylidene aniline 0.5 8 2,305 161 965 68 5 Cinnamylidene o-NO: aniline 0.5 8 2,620 183 1,080 76 170 6 CH;CH=NCH(OH1)4CH 0. 5 8 2, 740 192 650 230 r---| 7 COH13CH=NOH(CHI)ACH2 0.5 8 2, 900 202 430 30 300 l 7 8 (O|H5) C=NCH (011040111 0. 75 7 2, 860 200 880 62 190 r ---l 9 HOCONCH,(CH=)3CH:* 0. 25 7 2, 475 173 630 44 220 10. HOC0NHCH(CH )4CH* 0.25 7 2,900 202 520 36 300 11 Oiunamylidene methylamine 0.25 10 2,500 175 660 46 240 12 Cinnamylidene 2-OH-ethylamine-.. 0.5 7 2, 280 159 415 29 250 13--." Cinnamyljdene-2-methoxyethylamine. 0. 5 6 2, 151 455 32 200 14 Oinnamylidene trimethylene diamine 0. 5 7 2, 250 157 1, 400 98 140 15... CGH5 CH3) C=N(OH2)a-N=C (CH3)CuH5... 0. 5 6 1, 915 134 1, 270 89 16"--. [(CHahC (OH)CHzC(CHs)=NCH2]aCH2 0. 5 6 2, 200 154 1, 140 80 170 17.- C2H5C(CH3)=N'"NHC6H5 0.5 8 2,710 189 1,085 76 160 18 Isophthalyl hydrazide 0.5 8 2, 290 160 780 55 190 19..- Dimethyl glyoxime..- 0.2 12 2,375 166 940 66 170 20.-. OONCu as 1. 0 9 2, 400 168 1,450 100 140 21..... CmHznNCO 0.5 11 2, 500 1,650 114 140 1 No cure. After 24 hours at 205 C. Elongation at break.

*As piperidine salt. *As a eyclohexylamine salt.

TAB LE F Amine Molecular equivalent Run Amine weight weight 1 Cyclohexylamiue 99 99 2. 2-0 H-ethylamine 61 61 3- Cyclohexylamine. 99 99 4. nillne 93 93 5- o-NOz-auiline 138 138 6 Cyclohexylamine 99 99 7- -do 99 99 8 99 99 85 85 99 99 Methylamiue 31 31 2-OH-ethylam1ne. 61 61 2-methoxyethylami 75 75 Trimethylene diamin 74 37 do- 74 37 74 37 108 54 32 16 .33 33 20.- 532 266 21 CnHayNHz 269 269 EXAMPLE IX The data in Table G shows the use of hydroquinone and various quaternary compounds in a curable formulation containing no amine compounds. Low compression set values were obtained as reported. The amounts of the components in the formulation are given in parts by weight, and the quaternary components were used in about 25 percent solution in methanol.

EXAMPLE X The need for both a quaternary compound and an oxidizable aromatic hydroxy or amino compound is illustrated by the comparative data in Table H. All amounts are in parts by weight, and the quaternary compound was used in a 25 percent methanol solution. It is significant that quaternary compounds at the relatively low concentrations of this invention do not effect a cure when no oxidizable aromatic hydroxy or amino compound is present. The use of large amounts of curing agent (e.g. quaternary compound) to obtain reasonable cure rates, as is shown in US. 3,403,127, is undesirable because of high compression set and poor aging properties. Quantities are in parts by weight.

EXAMPLE XI The data in Table I illustrate the poor results obtained when no oxidizable aromatic hydroxy or amino compound is included in the formulation. No cure was obtained when only 1 part of the quaternary compound was used, and the cure obtained at the higher concentration of quaternary compound resulted in a product with 44 percent compression set. Runs 1 and 2 of Table -I correspond to Examples 1(b) and 1(c) in US. 3,408,127.

EXAMPLE XI I The data in Table I exemplify the use of several quaternary phosphonium compounds. All concentrations are in parts by weight, and the phosphonium compounds were in 25 percent methanol solution. Each run was milled on a rubber mill, molded for 30 minutes at 335 F. and post cured at 500 F. for 20 hours.

EXAMPLE XIII Runs illustrating the use of various amine compounds, including aromatic amines and tertiary amines, in the curable formulation along with the quaternary compound and oxidizable aromatic amino or hydroxy compound, are presented in Table K. The quaternary compound was in a 25 percent methanol solution. All concentrations are in parts by weight.

TABLE G Fluoroelastomer (CzFa/C F1= CH2, 24/76 mol ratio) 100 100 100 100 [(C4Ho)4N ][O 0113"] 0.4 4 o) 4 0 (30 5 1 0. 5 C4Ho) iN [OH-l 0. 4

i N-C OH- S C\ S O\ C H l( C4 0) 4N ]l 0. 5 Carbon black 30 30 30 30 30 Magnesium oxide 10 10 10 10 10 C8.(OH)1.... 2 2 2 2 2 Hydmqninnne 1 1 1 1 l C ure:

Sheet, 168 C. (30 minutes) Plug, 160 C. (30 minutes)- Post cure: 260 C. (20 hours) Compression set (percent): 400 F. (205 0.), 22 hours 7 7. 4 11 (1% (1% Mooney:

(10 Ft. rise at 121 0.), minutes 25+ 25+ 1. 4 25+ 25+ (p0 nt rise in 25 minutes at 121 C.) 4 0 4 2 Mooney, 335 F. (168 0.):

15 minute 3. 9 5. 4 0. 3 3.0 4. 7 (30 minute 4. 5 6. 1 0. 4 3. 3 5. 4 Original:

Tensile at break (p.s.l.) 2, 025 2, 1, 480 2, 000 2, Modulus at 100% elongation (p.s.1.) 1, 430 1, 325 1, 300 1, 445 1, 000 Elongation at break (percent) 140 Hardness, Shore A2 71 72 72 73 72 Heat aged (275 0., 72 hours) Tensile at break (p.s.i) 1, 410 1, 445 1, 400 1, 620 1, 490 Modulus at 100% elongation 1, 345 620 I 380 Elongation at break (percent) 115 90 90 100 120 Hardness, Shore Ar 83 81 84 80 79 TABLE I [Cure and post cure as in Table G1 TABLE H 1 2 1 2 3 5 Fluoroelastomer (C3Fo/CF2=CH2;24/76111011ati0) 100 100 Elastomer (Cam/OFFSET; 24 70 moi ratio) 100 100 100 K W HI I Q53 Tetrabutylammonium bromide. 0. 5 5 CH Hydroquinone 1.0 1.0

Carbon N-C/ CH Magnesium oxide 10 10 Calcium hydmm 2 2 2 1 onimrq s-o 0, 5g

81 Sheets, 168 0. (30 minutes) 0 CH Plugs, 160 C. (30 minutes) Post cure: 260 C. (20 hours) C 1(\Jaompression set, percent: 205 0., 22 hours.

ooney: Carbon black 3O 30 10 pt. rise at 121 C. minutes-.." 25+ 1 1 Point rise in 25 minutes at 121 0- 1 fi gg ggg gfi fi f 2 Mooney 3350 F' (168 4 4 (1) (1) Calcium hydroxide 2 2 15 minute 1 1 1 Compression set (percent) at 400 F. (24 hrs.) 6.5 4.2

n1]1nute Original:

Tensile at break( .s.i.) 2,004 2 140 Tensile at break "f 2g Modulus at 100% glongation (p.s.i.) '800 Modulus at 100% elongation 1 Elongation at break (percent) 190 Elongation at break (percent) 140 Hardness Shore 2 70 Hardness 71 (9 U Heat aged 3 F" 72 5 1' Heat aged (275D 5 1 3 5 (1) 1 Tensile at break (p.s.i.) 1, 360 1, 355 @fifgf at j 95 1 i Modulus at 100% elongation (p.s.i.) 1,180 765 d es ho 2 s1 (0 gg gg g g gggfi gra t); 13g 1 g Mooney: 10 pt. rise at 121 C minn 25+ N0 cure Mooney, 335 F.: I

25 15 minutes 4.6 7.7 *rninni'n 5.2 8.75

TABLE K Amino C-C11H:s Q N H: N N (Unfit):

HnN Z- Z N/ \N I H2C l CHz Ii 3 O H: H N-C NH: 0H 1 N mo 'crr z 2N(C a)a N C F IGF=CH1 elastomer (24/76 mol ratio) 100 100 100 100 100 100 W eig ht of amine 5 0.; 8.; 0. g 0.; 0,;

Tetrabutylammonium hydroxide. 0. (2 0. 0 $0 0. 0. 0 0Em carbon'blac o i) 10 i 10 Magnesium oxide. 1 1 1 1 1 1 Hydroquinone 2 2 2 2 2 2 Calcium hydroxide 9 8 5 7 8 5 14 Compression set (percent) (400 F.,24hrs.)-- 8 Original T nsile at break (p.s.i.) ,34 2,330 2, 640 2, 010 2, 560 Miodullfi at 12( ga 1 2, fgg 1, g 1, ggg 503 E on a. one. rea perce Hard ness, shoretga 77 69 70 65 80 65 0 a 0 a Har ess, Shore A: 80 72 76 68 94 60 What is claimed is: 1. An admixture curable in reactive association with TABLE I an inorganic acid acceptor capable of generating water 1 2 upon reacting with hydrogen fluoride to produce a cured elastomer having low compression set comprising the fol- Vinyiidene fluoridelhexatluoropropene copolymer 10 w lowing cgmponents;

cfligfifiiifii 2o 20 (a) An elastomeric copolymer of vlnylldene fluoride 1617155 3 1132? g g and at least one terminally unsaturated fluoromono- L -piienylene dimethylene bis(triethylammonium) olefin containing at least one fluorine atom substitu- 9 f 1 cut on each double bonded carbon atom, each carbeets, 168 0., 4511mm bon atom of said fluoromonoolefin being substituted g %%"g ,fi e fgga (1 hr) a C (1 hr) only with fluorine, chlorine, hydrogen or a lower 160 0. ('1 hr), 8010i ('1 hr.), 200 0. ('19 -1 fluoroalkylor fluoroalkoxy radical, at least 10 percent fi m g' (168 13.7 5 of the chain carbon atoms of sand copolymer bemg a0 minutes:IIIIII II I 22+ 9.8 CH units;

gg g ggi percent 205 24 0 44% (b) At least one quaternary compound of the formula Tensile at break (p.s.l.) I 1, 725 Modulus at 100% elongation (p s. 745 R QR QR [X zlm glorlrigationsafi' breXk (percent)- or at HESS Dre 2 Heat aged (278 0., 72 hours) [R Q R X Tensile at break (p.s.1. (i) 1, 300 gg fg g fl zg zf (P 8 3g whcrem Q is a nitrogen atom, R is an alkylene radical having from 2 to 12 carbon atoms or a phenylcumin sheet plug ene dialkylene radical having from 8 to 12 carbon atoms, R is an alkyl radical having from 1 to 12 carbon atoms or an aralkyl radical having from 7 to 12 carbon atoms, wherein R R and R are alkyl radicals having from 1 to 18 carbon atoms, X is an anion, and m is the valence of anion X; and

() At least one aromatic hydroxy or amino compound which has an oxidation potential no more than 1.5 volts with respect to a standard calomel electrode,

said curable admixture containing, per 100 parts by weight of said elastomeric copolymer, a concentration of said component (b) from about 0.05 to about 0.5 part by weight and a concentration of said component (c) from about 0.1 to about 2 parts by weight.

2. The curable admixture of claim 1 in which said mixture also includes from 0.1 to 2.5 parts by weight of (d) an aromatic amine, an aliphatic tertiary amine or a compound which is stable in the absence of water at temperatures below about 75 C. and which at temperatures above about 125 C. in the presence of water generates a basic nitrogen atom-containing compound having a pK in Water of no more than 14 and having at least one hydrogen atom bonded to said basic nitrogen atom.

3. The curable admixture of claim 1 in which said admixture also contains from about 2 to about 25 parts by weight, based on 100 parts by weight of elastomeric copolymer, of an inorganic acid acceptor capable of generating water upon reacting With hydrogen fluoride.

4. The curable admixture of claim 1 in which said elastomeric copolymer is an elastomeric copolymer of vinylidene fluoride and at least one comonomer selected from the group consisting of chlorotrifluoroethylene, perfluoropropene, l-hydroperfluoropropene and tetrafluoroethylene.

5. The curable admixture of claim 1 in which said elastomeric copolymer is an elastomeric copolymer of vinylidene fluoride and perfluoropropene.

6. The curable admixture of claim 1 in which said elastomeric copolymer is an elastomeric copolymer of vinylidene fluoride, perfluoropropene and tetrafluoroethylene.

7. An admixture curable in reactive association with an oxidizable aromatic hydroxy or amino compound and an inorganic acid acceptor capable of generating water upon reacting with hydrogen fluoride to produce a cured elastomer having low compression set comprising the following components:

(a) An elastomeric coplymer of vinylidene fluoride and at least one terminally unsaturated fluoromonoolefin containing at least one fluorine atom substituent on each double bonded carbon atom, each carbon atom of said fluoromonoolefin being substituted only with fluorine, chlorine, hydrogen or a lower fluoroalkyl or fluoroalkoxy radical, at least 10 percent of the chain carbon atoms of said copolymer being -CH units;

(b) At least one quaternary compound of the formula wherein Q is a nitrogen atom, R is an alkylene radical having from 2 to 12 carbon atoms or a phenylene dialkylene radical having from 8 to 12 carbon atoms, R is an alkyl radical having from 1 to 12 carbon atoms or an aralk-yl radical having from 7 to 12 carbon atoms, wherein R R and -R are alkyl radicals having from 1 to 18 carbon atoms, X is an anion, and m is the valence of anion X; and

(0) At least one aromatic amine, aliphatic tertiary amine or a compound which is stable in the absence of water at temperatures below about 75 C. and which at temperatures above about 125 C. in the presence of water generates a basic nitrogen atomcontaining compound having a pK, in water of no more than 14 and having at least one hydrogen atom bonded to said basic nitrogen atom, said curable admixture containing, per parts by weight of said elastomeric copolymer, a concentration of said component (b) from about 0.05 to about 0.5 part by weight and a concentration of said component (0) from about 0.1 to about 2.5 parts by Weight.

8. The curable admixture of claim 7 in which said admixture also contains (d) from about 2 to about 25 parts by weight, based on 100 parts by weight of said elastomeric copolymer, of an inorganic acid acceptor capable of generating water upon reacting with hydrogen fluoride.

9. The curable admixture of claim 8 in which said component (a) is magnesium oxide, lead oxide or dibasic lead phosphite.

10. The curable admixture of claim 7 in which said admixture also contains from about 0.5 to about 10 parts by Weight of an inorganic base, based on 100 parts by weight of said elastomeric copolymer.

11. The curable admixture of claim 7 in which said elastomeric copolymer is an elastomeric copolymer of vinylidene fluoride and perfluoropropene.

12. The curable admixture of claim 7 in which said elastomeric copolymer is an elastomeric copolymer of vinylidene fluoride, perfluoropropene and tetrafluoroethylene.

13. The curable admixture of claim 7 in which the amine or basic nitrogen-containing compound of component (c) has a molecular weight of not more than 1000 and an amine equivalent weight of not more than 500.

14. A process for curing an elastomeric copolymer of vinylidene fluoride and at least one terminally unsaturated fluoromonoolefin containing at least one fluorine substituent on each double bonded carbon atom, each carbon atom of said fluoromonoolefin being substituted only with fluorine, chlorine, hydrogen or a lower fluoroalkyl or fluoroalkoxy radical, at least 10 percent of the chain carbon atoms of said copolymer being CH units, which comprises:

(a) Admixing therewith from about 0.1 to about 2 pphr. of an oxizoable aromatic hydroxy or amino compound which has an oxidation potential no more than 1.5 volts with respect to a standard calomel electrode, from about 2 to about 25 pphr. of an inorganic acid acceptor capable of generating water upon reacting with hydrogen fluoride, and from about 0.05 to about 0.5 pphr. of at least one quaternary compound of the formula wherein Q is a nitrogen atom, R is an alkylene radical having from 2 to 12 carbon atoms or a phenylene dialkylene radical having from 8 to 12 carbon atoms, R is an alkyl radical having from 1 to 12 carbon atoms or an aralkyl radical having from 7 to 12 carbon atoms, wherein R R and R are alkyl radicals having from 1 to 18 carbon atoms, X is an anion and m is the valence of X;

(b) Subjecting said admixture to a pressure of between about 7 and 210 kg/cm. at a temperature of between about 95 C. and 230 C. for a period of between about 1 minute and about 15 hours, and

(c) releasing the pressure from said admixture and heating the resulting product at a temperature between about C. and about 315 C. for a period of between about 2 and 50 hours.

15. The process of claim 14 in which said oxidizable aromatic hydroxy or amino compound is hydroquinone.

16. The process of claim 14 in which said elastomeric copolymer is an elastomeric copolymer of vinylidene fluoride and at least one comonomer selected from the group consisting of chlorotrifluoroethylene, perfluoropropene, l-hydroperfluoropropene and tetrafluoroethylene.

17. The process of claim 14 in which said elastomeric copolymer is an elastomeric copolymer of vinylidene fluoride and perfluoropropene.

18. The process of claim 14 in which said elastomerio copolymer is an elastomeric copolymer of vinylidene fluoride, perfluoropropene and tetrafluoroethylene.

19. The process of claim 14 in which to said admixture is also added up to 2.5 pphr. of at least one aromatic amine, aliphatic tertiary amine or a compound which is stable in the absence of water at temperatures below about 75 C. and which at temperatures above about 125 C. in the presence of water generates a basic nitrogen atom-containing compound having a pK in water of no more than 14 and having at least one hydrogen atom bonded to said basic nitrogen atom.

References Cited UNITED STATES PATENTS 2'4 2,968,649 1/1961 Pailthorp et al 26080.5 3,051,677 8/1962 Rexford 26029.6 3,080,336 3/1963 Smith 26041 3,088,938 5/1963 Cluflf 26087.7 3,243,411 3/1966 Tawney et al. 260-6l 3,318,854 5/1967 Honn et al. 26087.7 3,403,127 9/1968 Flavell et a1. 26041 OTHER REFERENCES The O. G. Defensive Publication Keller, Def. Pub. of Ser. No. 608,999 filed Jan. 13, 1967, published in 856 O. G. 4, on Nov. 5, 1968,'Defensive Publication No. T 856,007, class 26087.7.

JOSEPH L. SCI-IOFER, Primary Examiner S. M. LEVIN, Assistant Examiner US. Cl. X.R. 26031.2 R, 32.8 R, 41 B, 41 C, 80.76, 80.77, 87.7

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION 9 Patent No. 3,655,727 Dated April 11., 1972 Inventor(s) Kalyanji U. Patel and John E. Maier Page 1 of 2 It is certified that error appears in the above-identified patent 9 and that said Letters Patent are hereby corrected as shown below:

Column 1 line 18 aromatic should be --elastomericn Column 1, line 21, 'elastomeric should be --aromatic-- Column 1, line TO, "and the polymers" should be --the polymers-- Column 5, line 5, "[(c H ,P+]BR-" should be -[(c h ,P+]Br--- Column 6, line 62, "6CH O LLNH should be --6CH O tNH Column 9, line 50, "or" should be --on- Column 10, line 35, "of-- should be inserted after "any" 5 Column 11, line 2, "was should be --are- Column 12, line 1, "cure" should be --cured-- Column 12, Table A, in item Com ression set: under Run V,

1 day at 400 F.(205 0.), "3' should be --6- Column 13, Table in middle of column, 8th item in Table, "Tensile strength at break, p.s.i. (kg./cm)A" should be --Tensile strength at break, p.s.i. (Kg./cm )A-- a Column 14, Table (1, line 7, "(C6H13CH=NCH2-)2CH" should be (c H cH=NcH 011 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 16553727 Dated April ll, 1972 Inventor(s) Kalyanji U. Patel and John E. Maier Page 2 of 2 It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 18, Table G, in item Compression set(percent) LOOF. (205C.),22 hours,

under t, "6.3/8' should be "6.3-- under 5, "6.3/8" should be --8-- Column 19, line 57, in Table I first item, "("Vitron A") should be Viton A")-- Column 20, Table K, in item "Heat aged(72 hrs at 528 F.)

under 6, Elongation at break(percent) 258 should be --250-- Hardness, Shore A "60" should be --68-- Column 22, line 1 4, in claim 9, "(a) should be --(d)-- Column 22, line 41, in claim 1 oxizoable should be --oxidizable Signed and Sealed this twentieth D3) OF April 1976 [SEAL] Attest:

RUTH C. MASON C. MARSHALL DANN Arresting Officer (mnmissimwr of Parents and Tradcmarkx 

